JPS6020439B2 - Additives useful in oily compositions - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION During the past decade, ash-free sludge dispersants have been used primarily as lubricants and agents in cleaning engine deposits and enabling extended crankcase oil drain periods. It has become increasingly important in improving the performance of gasoline.

Most commercially available ashless dispersants fall into several general categories. In certain categories, amines or polyamines may be used, such as those described in US Pat. No. 3,275,555.
No. 4, No. 3565592 and No. 356 No. 04, the halogenated olefin polymer is bonded directly to a long chain hydrocarbon polymer (usually polyisobutylene) by reaction with a polyamine. In cases falling into other categories, polyamines are
No. 8, No. 3,219,666, etc., by forming amide or imide bonds, long-chain monocarboxylic acids (see, e.g., U.S. Pat. It is attached to polyisoptylene via an acid group such as a chain dicarboxylic acid. More recently, nitrogen-free and ash-free dispersants have been developed, as described in U.S. Pat. formed by esterification. The reaction products of hydrocarbon-substituted succinic anhydrides, such as the polyisobutenyl succinic anhydride described above, with compounds containing both amine and hydroxyl groups have been suggested or investigated in the prior art.

For example, U.S. Pat. No. 3,272,746 discloses the use of ethanolamine and jetanolamine and N-(2-hydroxyethyl)ethylenediamine, N,Z-bis(2-hydroxyethyl) to obtain ashless dispersants for lubricating oils.
He teaches the reaction of various hydroxyalkyl layered alkylene amines, such as ethylene diamine, with alkenylsuccinic anhydrides. In U.S. Pat. No. 3,324,033, a hydroxyamine such as jetanolamine is reacted with a long chain alkenyl succinic anhydride to form a mixture of esters and amides, where some portion of jetanolamine is The hydroxyl group reacts to give an ester bond, while the other part of the jetanolamine forms an amide bond. US Patent No. 3364
No. 001 teaches tertiary alkanolamines reacted with alkenylsuccinic anhydrides to form esters useful as gasoline additives. No. 48,049', dispersions in lubricating oils and fuels made by esterifying alkenylsuccinic anhydrides with hydroxy compounds made by reacting alkanolamines with unsaturated esters, amides or nitriles. teaches anti-corrosion agents, corrosion inhibitors and anti-wear additives.

US Pat. No. 3,630,904 teaches the reaction of hydroxyamines with both short chain and long mirror dicarboxylic acids. U.S. Pat. No. 3,784,374 teaches polymeric condensation products of polycarboxylic acids or anhydrides with various alkanolamines such as aminoethylethanolamine, N-methyljetanolamine, and the like. US Patent No. 3
No. 576,743 teaches the reaction of polyisobutenylsuccinic anhydride with a polyol such as pentaerythritol followed by trismethylolaminomethane (THAM) (see E. Somplel). U.S. Pat. No. 3,632,511 discloses a polyisobutenylsuccinic acid surprise containing polyamines and polyhydric alcohols (including THAM).
It teaches how to react with both. U.S. Patent No. 36974
No. 28 (E-Mmplell) teaches the reaction of polyisobutenylsuccinic anhydride with a mixture of pentaerythritol and THAM. As mentioned above, the prior art
Dispersants are taught formed from long chain hydrocarbyl-substituted dicarboxylic acid materials (usually alkenylsuccinic anhydrides) reacted with various amino or hydroxyl compounds through amide, imide or ester linkages.

Contrary to this prior art, the present invention provides that the reaction of long chain hydrocarbyl dicarboxylic acid materials, i.e. acids or anhydrides or esters, with certain amino alcohols under certain conditions may result in different types of bonds. It is based on the discovery that substances containing oxazoline bonds are highly effective as detergents or dispersants for oily compositions such as lubricating oils and gasoline. The long mirror hydrocarbyl layered dicarboxylic acid material used in the present invention, i.e.
Acids or anhydrides or esters are substituted with long hydrocarbon chains, typically olefinic polymer chains, such as fumaric acid, itaconic acid, maleic acid, maleic anhydride, chlormaleic acid, dimethyl fumarate, etc. Q,8-unsaturated C
4~C,.

Manufactured from dicarboxylic acids or their anhydrides or esters. In turn, these hydrocarbyl-substituted dicarboxylic acid materials and their preparation are well known in the art, see, for example, US Pat. No. 3,219,666, US Pat. No. 3,172,892, US Pat.

The hydrocarpyl moiety should have an average of at least 5M solid aliphatic carbon atoms per dicarboxylic acid group and be substantially saturated.

Excessive unsaturation in the final product tends to oxidize in the engine and form excessive gums and resins, so typically no more than 10 mole percent, and preferably no more than 5 mole percent, of the total carbon-to-carbon bonds are present. It is unsaturated. A more detailed description and examples of hydrocarbyl substituent moieties can be found in U.S. Pat. No. 32,727.
No. 46, column 2, line 35 to column 4, line 10. These hydrocarbyl-converted dicarboxylic acid materials are now prepared by reacting an unsaturated dicarboxylic acid material (usually maleic anhydride) with an olefin (usually an olefin polymer still retaining terminal unsaturation).

The olefin polymer is first halogenated, if desired,
For example, chlorinating or brominating to about 2-5% chlorine or about 4-8% bromine by weight based on the weight of the fleas;
It can then be reacted with non-maleic acid (see US Pat. No. 3,444,13). In some cases, the olefin polymer may be fully saturated, such as ethylene-propylene copolymers made by Ziegler-Natta synthesis using hydrogen as a modifier to control molecular weight. good.

In the case of such saturated polymers, the polymer can be halogenated to make it reactive, and this can be condensed with an unsaturated dicarboxylic acid material, which Added randomly along the chain. Preferred olefin polymers for reaction with unsaturated dicarboxylic acids are polymers consisting of high molar amounts of C2-C5 monoolefins, such as ethylene, propylene, butylene, isobutylene and pentene. The polymer is
It can be a homopolymer such as polyisobutylene, and a copolymer of two or more of these olefins, such as a copolymer of ethylene and propylene, or butylene and isoptylene. Other copolymers include those in which a small molar amount of the copolymer monomer, for example 1 to 20 mol %, is C4-C,8 non-conjugated diolefin, such as copolymers of isobutylene and putadiene, ethylene, propylene and 1,4
-Includes copolymers of hexadiene and the like. Olefin polymers typically have number average molecular weights ranging from about 750 to about 200,000, and even from about 1,000 to about 20,000.

Particularly effective olefin polymers have number average molecular weights in the range of about 900 to 3000 and about one terminal double bond per polymer chain. A particularly useful starting material for the high performance dispersant additives prepared according to the present invention is polyisobutylene. Particularly effective when it is desired that the dispersant additive also has viscosity index improving properties are 10000-200000, e.g. 25000-10
It is a polymer with a number average molecular weight of 0,000.

Particularly preferred examples of such viscosity index improving polymers are:
It is a copolymer of about 30-85 mole percent ethylene, about 12-70 mole percent C3-C5 mono-Q-olefin, preferably propylene, and 1-20 mole percent C4-C,4 nonconjugated diene. These ethylene-propylene viscosity index improving copolymers or terpolymers are usually Ziegler-improving copolymers or terpolymers.
produced by Natta synthesis (e.g., U.S. Pat. No. 35
51336). Some of these copolymers and terpolymers, such as ethylene, propylene and 5
- elastomeric terpolymers of ethylene, norbornene, and terpolymers of ethylene, propylene and 1,4-hexadiene. Other halogenation techniques for attaching dicarboxylic acid materials to long hydrocarbon chains include
Either by first halogenating the unsaturated carboxylic acid material and then reacting it with the olefin polymer, or by bubbling a halogen gas, e.g., chlorine, into the mixture of the polyolefin and the unsaturated dicarboxylic acid material, and then
20 qo to remove HCI gas (e.g., U.S. Pat. No. 3,381,022 and U.S. Pat.
(See issue 04).

The amino alcohol used to make the oxazoline dispersant has 2 to 3 hydroxyl groups, contains a total of 4 to 8 carbon atoms, and has the following formula [herein
is an alkyl or hydroxyalkyl group, and
at least one of the substituents, preferably both X substituents, is a hydroxyalkyl group of the structure -(CH2)nOH, where n is 1 to 3. -2-amino-1-alkanol.

Examples of such 2,2-disubstituted amino alcohols include 2
-Amino-2-methyl-1,3-propanediol, 2
-amino-2-(hydroxymethyl)-1,3-propanediol (also known as tris(hydroxymethyl)aminomethane or THAM), 2-amino/-2-ethyl-1,3-propanediol, and the like.

THAM is particularly preferred for reasons of effectiveness, availability and cost). The formation of conventional oxazoline dispersants in very high yields, in the presence or without an inert diluent,
About 1 to 2 molar equivalents of the 2,2-di-amino-1-2-amino-1-alkanol are added per mole of dicarboxylic acid material, and the mixture is heated to 140-240°C, preferably 1
0.5 to 2 at 80 to 0°C, more commonly 2 to 2
This can be done by heating for 8 hours.

Although not required, a small amount, e.g. 0.01-2% by weight, preferably 0.1-1% by weight based on the weight of the reactants, of a metal salt may be used as a catalyst in the reaction mixture to control the reaction time. It can be shortened.

The metal catalyst can be subsequently removed by filtration or by washing the product hydrocarbon solution with a lower alcohol or alcohol/water solution, such as methanol, ethanol, isopropanol, and the like. Alternatively, the metal salt can remain in the reaction mixture as it appears to be stably dispersed or dissolved in the reaction product;
Depending on the metal, it may also contribute to oil or gasoline performance benefits.

This is believed to occur due to the use of zinc catalyst.
Inert solvents that can be used in the above reactions include hydrocarbon oils such as mineral lubricating oil, kerosene, neutral mineral oil, xylene, halogenated hydrocarbons such as carbon tetrachloride, dichlorobenzene, tetrahydrofuran, and the like.

Metal salts that can be used as catalysts in the present invention include Zn, Co,
Includes Nh and Fe carponates.

Metal catalysts derived from strong acids (HC1, sulfonic acids, &S04, HN03, etc.) and bases tend to reduce the yield of oxazoline products while allowing imide or ester formation. For this reason, these strongly acidic or basic catalysts are not preferred and are usually avoided. The carboxylic acids used to prepare the desired catalyst are C, ~C,
8, such as C, to C8 acids, such as saturated or unsaturated aliphatic hydrocarbon mono- and dicarboxylic acids, especially fatty acids. Specific examples of such desirable carboxylate salts are:
Includes zinc acetate, zinc formate, zinc propionate, zinc stearate, manganese acetate (contains manganous), iron tartrate, cobalt acetate (contains cobaltous), and the like. Competition of the oxazoline reaction can be easily confirmed by using infrared spectroscopy to follow oxazoline formation (the oxazoline peak appears at 6.0 fres) or by the cessation of water evolution.
Although not known with complete certainty, based on experimental evidence, hydrocarbyl-substituted dicarboxylic acid materials of the invention, such as hydrocarpyl-substituted succinic anhydrides, and amino alcohols, such as tris-hydroxymethylaminomethane (THAM) Reaction with 2 equivalents of 2,2-disubstituted-2-amino/ethanol such as 2,2-disubstituted-2-amino/ethanol gives the oxazoline, e.g. bis-oxazoline, via the mediation of several distinct reactive species.

If an acid anhydride is used, the initial conversion would involve cleavage of the anhydride by the amino functionality of one mole of aminoalcohol to form the amicacid. Addition of one more molar equivalent of the amino alcohol would produce an amine salt of the amino acid, which would then undergo cyclodehydration on further heating to the final bis-oxazoline product. The catalytic effect of metal salts such as zinc acetate (ZOAc2) on oxazoline formation appears to be highly attributable to the favorable polarization of the hydroxy functionality of the aminoalcohol reactant. These reactions can be written as follows in the case of bis-oxazoline. (where R is the hydrocarbyl group of succinic anhydride and tris-hydroxymethylaminomethane (
Contrary to the above oxazoline formation using disubstituted amino alcohols (where each X represents a -C-OH group when using THAM), when the amino alcohol has no substituent as in 2-aminoethanol or Amino alcohols are Does not undergo the oxazoline reaction described above.

Instead, these other amino alcohols react almost exclusively with succinimide to give succinimide products, as exemplified in the reactions below. Experiments on the above reactions (where R and

The oil-soluble oxazoline reaction products of the present invention can be incorporated into a wide variety of oily compositions.

They are used in lubricating oil compositions such as automotive crankcase lubricants, automatic transmission fluids, etc., for all compositions.
Generally about 0.01-2% by weight, such as 0.1-1% by weight, preferably 0.3-3. can be used at concentrations within the range of % polymerization. Lubricants to which oxazoline products can be added include not only hydrocarbon oils derived from petroleum, but also polyethylene oils, alkyl esters of dicarboxylic acids, esters of dicarboxylic acids, pyrogallol, and alcohols, carbonic or phosphoric acids. Also included are synthetic lubricating oils such as alkyl esters, polycicolines, fluorocarbon oils, mixtures of mineral lubricating oils and synthetic oils in any proportion. The additive may be a concentrate formed by dissolving a small proportion, e.g. 2 to 45 parts by weight, of the additive in a large proportion, e.g. 1 to 55 parts by weight, of mineral lubricating oil, with or without the presence of other additives. It can be conveniently mixed as

In the above compositions or concentrates, dyes, pour point depressants,
Antiwear agents such as tricresyl phosphate or dialkylzinc dithiophosphates having 3 to 8 carbon atoms in each alkyl group, ethylene-propylene copolymers, polymethacrylate, polyisoptylene, alkyl fumarate-vinyl acetate copolymers Viscosity index improvers such as polymers, and other ashless dispersants, detergents and viscosity index improvers may be present.

Production Example of Bis-Oxazoline Additive Example 1 A bis-oxazoline of polyisobutenylsuccinic anhydride and tris-hydroxymethylaminomethane was produced as follows.

Take out 280 g (0.5 equivalent) of polyisobutenyl succinic anhydride (PI spot A) from the bottom, a thermometer, a hollow funnel,
A laboratory glass 11 reaction flask equipped with a nitrogen outlet and an overhead condenser with a Gene-Stark water trap was charged.

The flask was heated over oil. The anhydride was then heated to about 200° C. under a nitrogen atmosphere. While at this temperature, 0.5 moles (60.5 moles) of tris-hydroxymethylaminomethane (THAM) was added at about 5 moles each over a period of 1 hour. After that, the reaction was continued for 2 hours at 200 oo while collecting water from the condenser and observing the reaction. The flask was then allowed to cool and 11 parts of hexane was added to the flask to dissolve the reaction product, which was then drained from the flask and filtered through furnace paper to remove solids. The hexane solution was then washed three times with 250 g of methanol. Thereafter, the hexane layer was placed in a 9-piston rotary evaporator for about 2 hours to evaporate the hexane. Then an equal weight of a neutral mineral lubricating oil (Solvent 150Ne Yamara) having a viscosity of about 15 mm at 10 F is added.
1) was added under the flask to give a bottle concentrate containing about 5% by weight oxazoline reaction product in about 5% by weight mineral lubricating oil. The infrared spectrum of this concentrate product showed a strong absorption band at about 60 peaks, as expected for bis-oxazoline. The product Solvent 15% active ingredient (50% active ingredient in raloil) was analyzed to be 0.7% nitrogen and 2.30% by weight. The observed oxygen to nitrogen (0/N) ratio of 2.95 is in close agreement with the theoretical 0/N ratio of 3. The product exhibited a total acid number (ASTM-D664) of 0.03. The polyisobutenyl succinic anhydride used above can be prepared using well-known techniques, viz.
Based on the weight of chlorinated polysoptylene, approximately 3. Chlorine content in mother weight % and on average in polyisobutylene groups 7
It was produced by reacting chlorinated polyisobutylene having M solid carbon atoms with maleic anhydride at about 200 qo.

The resulting polyisobutenyl succinic anhydride has an oKO of 80
The saponification value (Sap.NO) of H. nota is shown. Example 2 Polyisobutenyl succinic anhydride with 8 ap-NO of 5002 (0.78 equivalents), where the polyisobutenyl group has on average about 70 carbon atoms, 500
'tetrahydride as a solvent.

A mixture of furan (THF), 4 hours of zinc acetate dihydrate (Zn~2.bait 20) as a catalyst and 96.8 hours (0.8 mol) of tris-hydroxymethylaminomethane (THAM) was added as described above. A glass reactor was charged and heated. When the reaction temperature rose to 720°C, the THF solvent was allowed to run out. Further heating at about 200 qo for 4 hours provided the expected amount of water in the trap, ie about 1.1 moles of water. After filtration, the reaction product was analyzed to contain 1.99% nitrogen and 0.12% zinc by weight. The product was drained from the flask and added with an equal volume of Solve for testing in the Sludge Inhibition Bench (SIB) test described below.
Diluted with NT15 EUOAL mineral lubricating oil. Example 3 A mixture of 500 g (0.78 eq.) of the polyisoptenyl succinic acid dihydrate of Example 2, 968 g (0.8 mol) of tris-hydroxymethylaminomethane and 4.0 g of zinc acetate dihydrate was added to the The mixture was poured into a glass reactor.

The mixture was heated in an oil bath at about 200-220 qo for about 3 hours until water stopped evolving from the reactor.
Approximately 18.09 (1 mole) of water collected in the trap.
The infrared spectrum of the reaction product discharged from the flask showed a strong absorption band at 6.0 μm, indicating the formation of an oxazoline structure. Elemental analysis shows that 5 wt% So
The final product of 5% by weight of the reaction product dissolved in lvent15 state e mountain 1 oil is 1.08% nitrogen and 0.0 bulb%
of zinc. Example 4 60.571 b (27.5 mol) of the polyisobutenyl succinic anhydride of Example 2, 11.7 b (27.5 mol) of THAM and 0.49 b (1 mol) of zinc acetate dihydrate as catalyst The salt mixture was introduced into a small pilot plant condensed reactor equipped with a nitrogen purge, a blower, and an overhead condenser with a water trap.

The reaction mixture was heated to 220° C. at a rate of 50 qo/hour and kept at that humidity until 3.39 b (theoretical 84.49 mol) of water of reaction was formed. Thereafter, the reaction contents were cooled and added to the Solvent 15 state etra.
1 oil to give a 5% by weight solution of the reaction product.

The full concentrate exhibited a hydroxyl number of 37.0 and contained 0.92% nitrogen and 0.05% zinc, based on the weight of the concentrate. Examples 5-23 Using the same general method as described in Example 3, 980 and 1
Various polyisobutenyl succinic anhydrides (PI spots A) of polyisobutylene having a number average molecular weight of 8000,
2-amino “2-methyl-1-ph.

. Panol (AMP), 2-amino-2-methyl-1,
3-propanediol (AMPD) and 2-amino-2
-Hydroxymethyl-1,3-pro/gundiol (T
The bis-oxazolines were formed by reacting with 2 molar equivalents of various amino alcohols, including HAM). Examples 1-2
The reactants, proportions, and product analysis of 3 are summarized in Table 1.

Table 1 (a) Molecular weight of polybutenyl group (PIB) in vapor pressure osmosis (VPO) (c) Zinc acetate dihydrate (d) 5
(e) THF used to dissolve rHAM; (f) 20 wt. solution of oxazoline reaction product dissolved in SI50N (g) Solvent 150 Neutral mineral lubricating oil. ) 30.3 minutes of rHAM added over 1 hour followed by 24.51 hours of AMP added over 1 hour Example 1 A number of additives of the present invention were subjected to Sludge Suppression Bench (SB) testing, which , after numerous evaluations, was found to be an excellent test for evaluating the dispersing power of dispersing additives for lubricating oils.

The vehicle chosen for the sludge control tabletop test is used in taxis that are commonly driven for short distances only, and thus has a raw viscosity of approximately $32 US at 1000F with a high concentration of sludge precursor deposited. It was a mineral lubricating oil composition for used crankcases.

The oil used contained only a refined base mineral lubricating oil, a viscosity index improver, a flow reducing agent, and a zinc dialkyldithiophosphate antiwear additive. This oil sludge contained no dispersant. A certain amount of such oil used is 100
Obtained by draining and recharging a taxi crankcase at 0-2000 mile intervals. The sludge suppression tabletop test is conducted in the following manner.

The used crankcase oil, which is milky brown in color, is about 3
Sludge is removed by centrifugation for 1 hour at 9000 m2. The resulting clear red supernatant oil is then decanted and separated from the insoluble sludge particles. However, this kerosene still contains oil-soluble sludge precursors that are more likely to form oil-weak deposits of sludge when heated under the conditions used in this test. The sludge control properties of the additives to be tested are determined by adding a small amount of the particular additive to be tested, for example 0.3, 0.51 or 2% by weight based on active ingredient, to a fixed proportion of the supernatant working oil. Determined by Each blend to be tested for 10 days was placed in a stainless steel centrifuge tube and heated for 28 hours in the presence of air.
Heat at 00F for 16 hours.

Following heating, the test tube containing the oil to be tested is cooled and then centrifuged for 30 minutes at approximately 39,000 °C.
Any deposits of fresh sludge produced in this step are separated from the bottle by decanting the top kerosene, and the sludge deposits are then carefully washed with 25' pentane to remove all residual oil from the sludge. do.
The weight (in female numbers) of the new solid sludge produced in this test is then determined by drying and weighing the residue. The results are recorded as the number of sludge traces per 1000 g of oil, thus measuring the difference of 1 part per 1000 mts. The less new sludge produced, the more effective the additive is as a sludge dispersant. In other words, if the additive is effective,
It is stably suspended in oil. It retains at least a portion of the new sludge that forms upon heating and oxidation, so that it does not settle during centrifugation. The above test was used to compare the dispersion performance of the oxazoline additive of the present invention to that of a commercially available dispersant (referred to as PIBSA/TEPA).

PIBSA/TEPA was prepared by the reaction of 1 mole of tetraethylenebentamine with 2.8 moles of polyisobutenyl succinic anhydride obtained from polyisobutylene with a number average molecular weight of about 1000. This PI mother A/TEP
Dispersant A was used in the form of an additive concentrate containing approximately 5% polymerization in a 5% by weight mineral lubricating oil. This PI
Analysis of the pre-existing A/TEPA additive concentrate yielded 1.14% nitrogen, indicating that the active ingredient, ie, PIBSA/TEPA itself, contained approximately 2.28% nitrogen. All of the additive concentrates described below were used in amounts sufficient to provide 1.0, 0.5, and 0.3 weight percent effective additive to make the test blends. Omotekawa will show you the test results. Table O From Table B, it is shown that the dispersant of the present invention was used in commercially available PI spots A/TE, which are widely used in crankcase lubricating formulations.
It can be seen that it was more effective than PA.

In particular, 1. of PmSA/TEPA itself (i.e.,
The 5 wt.% concentrate (2 wt.%) gave 5.2 9 new precipitated sludge per 10 night crankcase oil. On the other hand, the bis-oxazoline products of the present invention shown here stably suspend the fresh sludge of Taoyama, as shown by the fact that they do not significantly settle the sludge during centrifugation. Therefore, it was more effective as a sludge dispersant. Similar results are 0.
5% by weight and 0. The amount of active ingredient is expressed in round weight %. Lubricant A: This was an SAE Grade 30 crankcase lubricant formulation for automotive crankcase specifications used as a control.

This control formulation contained mineral lubricating oil, 4. Iso weight% P
IBSA/TEPA ashless dispersant concentrate and a series of well-known additives: P2-treated Q-pinene as an oxidation and corrosion inhibitor, zinc dialkyldithiophosphate, and barium sulfonate as a detergent inhibitor additive. and an overbased barium detergent consisting of barium carbonate formed in the presence of P2S5-treated polyisobutylene, an alkylphenol as a surfactant, along with anti-rust additives.

Lubricants B to E: These lubricants are different from the above-mentioned lubricant A in 4. Total amount%
were identical, except that the weight percent concentrate of PI Spot A/TEPA Ashless Dispersant 5 of Example 4 was omitted and the inventive oxazoline dispersant of Example 4 was used in different amounts as follows.

Lubricant B - 4% by weight concentrate of oxazoline 5 of Example 4.
Total weight%: Lubricant C-37 Weight%: Lubricant D-3.2
5% by weight; Lubricant E-2.75% by weight. The aforementioned lubricant A
-E were tested in the VC engine test according to the MS rank well known in the automotive industry as described in ASTM Special Publication 315-E, "Multiple Cylinder Test Procedures for Evaluating Automotive Engine Oils."

At the end of each test, various parts of the engine were rated on a 1-10 rating scale. Here, 10 represents a completely clean part, while 4 points represents an increase in the degree of deposit formation. The various scores are then summed up to give a complete score of 10.
Averaged based on. The results obtained for the above composition are shown on the front side. Table X As can be seen from Table m, the two engine experiments were
/TEPA-containing formulations.

However, considering the two experiments for Lubricant A, the bis-oxazoline dispersion of Example 4 was 4.68 and 37.
It can be seen that the oxazoline has an excellent concentration in weight percent, indicating high effectiveness of this oxazoline. Considering varnishes, oxazolines, even in an amount of 3.25% by weight, are
A and in an amount of 2.75% by weight (i.e.
1. (wt% active ingredient) were almost as effective. Therefore, ÷oxazoline dispersants were very effective in important industrial tests. The results of these engine tests show that the oxazoline additive of the present invention is not only a good sludge dispersant, as indicated by the sludge rating, but also reduces varnish deposits (varnish rating) on various engine parts, especially pistons. It is shown to have a good oxidation inhibiting effect as shown by the reduction of varnish deposits on the skirt (piston skirt varnish rating). The favorable antioxidant properties of this oxazoline dispersant additive reduce the need for additional conventional antioxidants. Caterpillar 1-H test (Skin L
-L-210 crab). Table W below lists the results of the above engine tests for each lubricant and indicates piston cleanliness. Table N [11] Requirements are estimates; actual testing of the piston is performed by certification; slight deviations from the stated limits are allowed based on the overall condition of the piston.

As can be seen from Table W, lubricant B containing an oxazoline dispersant was found to have a large amount of One of the two experiments was nearly passed due to the deposit below the second groove section (bottom), although it gave an unusually low deposit on the window as shown.

However, this can be overcome by changing the formulation. Example 2 Part A 350 mols (0.328 moles) of polyisobutenyl succinic anhydride having an ASTM saponification number of about 105 and a molecular weight of about 1067 were prepared as follows:
mol) of 2-amino-2-hydroxymethyl-1,3-propanediol (THNM).

Polyisobutenyl succinic anhydride and THAM were stored in two 4-necked flasks equipped with a thermometer, a strainer, a dropping funnel, a condenser with a Sheen-Stark water trap, and an inlet for nitrogen to provide a nitrogen atmosphere. 'Dissolved in xylene. Approximately 145-15 over 1 hour 45 minutes
Approximately 9 cc of water collected in the trap upon heating up to 20°C.

Heating was then stopped overnight and the next day the reaction mixture was refluxed for an additional hour at 153°C, with 10 cc of water now built up in the trap. The reaction mixture was then purged with nitrogen to evaporate the xylene, while the temperature rose to 1°C. This system is then connected to a vacuum pump and the
It was heated at about 182°C to 1°C for 3 hours under a pressure of 30° Hg. Heating was then stopped overnight. The next day, the xylene-free mixture was clarified to 10°C and 489 cc (419 g) of xylene was added to make a concentrate containing 5% by weight of the bis-oxazoline reaction product dissolved in xylene.
1.23 for a calculated nitrogen content of 1.1% by weight
A concentrate with a nitrogen content of % by weight was obtained. An 8 part SI master test was conducted on the above Part A product to determine its effectiveness as a sludge dispersant in lubricating oils.

- Two blank experiments were first conducted using Sm oil without additives. The blank test gave 17.1 wp and 2.7 wp of sludge per 10 liters of oil, respectively, thus clearly showing that the above reading of 2.7 is erroneous and can be ignored. SIB test pond and concentrates in part A (
Blends with 50%) oxazoline) 0.25 wt%, 0.5 wt% and 0.75 wt% are each 9. It gave a reading of 9 of 0.3 and 0.1 of sludge. The oils without additives gave readings of 16-17, so the treated oils showed that the oxazoline concentrate was effective as a dispersant and contained 0.50 and 0.75% by weight.
It was shown to be extremely effective at low concentrations. The SIB test was repeated again later.

Here, a series of four blank experiments, i.e., untreated oil experiments, were carried out with sludges of 16.4 c, 17.2 c, 18.1 c and 17.8 o per 10 min of oil, respectively. gave the reading. Two tests of SIN oil containing 0.25% by weight Part A concentrate gave readings of 12.2 and 12.0. Two tests of SB oil containing 0.50% by weight of the concentrate gave readings of 3.1 and 6.1.

Tests at 0.75 wt% and 1 wt% concentrate both gave readings of 0.1.

1.5% by weight concentrate gives a reading of 0.7 and 2. of concentrate gave a reading of 0.6.

All of the above readings are expressed in 9 parts of sludge per 10 parts of the test oil. Outside of this test data, the above SIB test data for the bis-oxazoline product of Part A was found to have a concentration level of about 0.75% by weight, i.e. about 0.3%.
This confirms that 75% by weight active ingredient represents a highly effective sludge dispersion. Example 243
2 parts (0.03 mol) of polyisobutenylsuccinic anhydride having a molecular weight of about 1067 were mixed with 7.2 parts (0.06 mol) of 2-aminohydroxymethyl-1,3-probanediol and 100 parts of polyisobutenyl succinic anhydride having a molecular weight of about 1067. The reactants were reacted by mixing them with 25 units of xylene in a 3-necked flask.

Raise the temperature to 9$0 for 1 hour, then stop heating,
The mixture was allowed to grow until the weekend. Following this, the mixture was heated again to 93° C. with stirring for 3 hours. The temperature was then raised to 191° C. and the contents were flushed with nitrogen to remove the xylene. After xylene removal was complete, the mixture was vacuum stripped under two sides of Hg pressure at 191° C. for 3 hours to remove the water produced. The reaction mixture was allowed to cool overnight while maintaining vacuum. The product was collected from the flask the next day. The product was analyzed to be 2.2 wt. % nitrogen compared to a calculated value of about 2.2 wt. % nitrogen for the bis-oxazoline. Several mono-oxazo. A phosphorus dispersant was prepared as follows.

Reference Example 1 Approximately 0.2 mol of polyisobutenyl succinic anhydride (S
ap. ship. 80) into the reactor and put it under nitrogen atmosphere for 2 hours.
It was heated to 0.5 qo.

To the reactants was added 0.2 moles (24.2 molar) of tris-hydroxymethylaminomethane in portions over an hour. Thereafter, this mixture was allowed to sail at 20 psi for about 3 hours while water was being drained from the reactor. Once cooled, half of the reaction mixture was dissolved in an equal volume of % Solve.
Dissolved in nt15 state e mountain ral oil.

The resulting oil solution was then diluted with 500 °C of hexane and the resulting hexane solution was washed three times with 250 °C of methanol each. Rotary evaporation of the hexane layer yields
The concentrate was analyzed to give 0.5% nitrogen and 2.37% oxygen by weight and a TAN (total acid number) of 0.16. The experimentally found O/N ratio of 4.7 is 46
This was in very good agreement with the theoretical ○/N ratio.

Furthermore, the strong absorption band at peak 60 in the infrared spectrum of this product indicated that a monooxazoline structure was produced. Another strong absorption band at 5.75 μm indicated that an ester structure was also formed.

This appears to be between one hydroxyl group extending from the oxazoline ring and the carboxyl group of the polyisobutenylsuccinic anhydride. Reference example 2 Approximately 80 Sap. No. Polyisobutenyl succinic anhydride having a temperature of 1335 mm was charged to a four-necked flask and heated to 205 mm.

The reactants were flushed with nitrogen and 121 g of tris-hydroxymethylaminomethane was added over 1 hour, being careful to avoid foaming. The course of the reaction was observed by infrared spectroscopy, which showed that the reaction was essentially complete after 8 hours. The pure product analyzed to be 1.12% nitrogen by weight and had a number average molecular weight (by vapor pressure osmosis) of 3034. The infrared spectrum of the product showed the expected ester and oxazoline absorption bands at peaks 575 and 6.02, respectively. Reference example 3 Sap No. 3 of about 80. 53.4 Zb polyisobutenyl succinic acid bran hydrate (PI Spot A) was placed in a reactor and heated to 4350F.

PIBSA reactant was washed and flushed with nitrogen, 4.84
Tris-hydroxymethylaminomethane (b) was added over 1 hour. The reaction continued until water evolution ceased. The product was diluted with an equal weight of Solvent 15 state oil and showed ester and oxazoline absorption in the infrared spectrum. In addition, 50 to 140 hardness, preferably about 60 to 30
of solid carbon atoms should be present.

Therefore, in the case of very high molecular weight polymers, they are commonly chlorinated to add multiple dicarboxylic acid groups along the chain. For example, if a polymer with 1000 solid maleic anhydride atoms is used, it is chlorinated and then treated with maleic anhydride to randomly distribute about 5 solid maleic anhydride units along the polymer chain. These maleic anhydride units are then converted into mono- or bis-oxazoline units or a mixture of mono- and bis-oxazoline units. In summary, useful additives for oily compositions include a hydrocarbon-substituted dicarboxylic acid material and a 2,2-disubstituted-2-amino-1-alkanol in which a substantial proportion of the amino-alkanol is an oxazoline. Esther, as simple as converted into a ring;
can be prepared by reacting under conditions such that imide or amide formation is eliminated or at least minimized.

Claims (1)

[Claims] 1 A large amount of lubricating oil and 0.01 to 20% by weight (based on the total composition) of the following structural formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X is an alkyl or hydroxyalkyl group, where the alkyl group has 1 to 3 carbon atoms, and at least one of the X substituents on each ring
is a hydroxyalkyl group of the structure -(CH_2)_nOH, where n is 1 to 3, and R is a substantially saturated hydrocarbyl group having at least 50 carbon atoms. oil composition.